U.S. patent application number 12/534436 was filed with the patent office on 2010-03-04 for amorphous oxide semiconductor and thin film transistor using the same.
This patent application is currently assigned to CANON KABUSHIKI KAISHA. Invention is credited to Ryo Hayashi, Hideya Kumomi, Hideyuki Omura, Yuzo Shigesato.
Application Number | 20100051938 12/534436 |
Document ID | / |
Family ID | 41426348 |
Filed Date | 2010-03-04 |
United States Patent
Application |
20100051938 |
Kind Code |
A1 |
Hayashi; Ryo ; et
al. |
March 4, 2010 |
AMORPHOUS OXIDE SEMICONDUCTOR AND THIN FILM TRANSISTOR USING THE
SAME
Abstract
There is provided an amorphous oxide semiconductor including
hydrogen and at least one element of indium (In) and zinc (Zn), the
amorphous oxide semiconductor containing one of hydrogen atoms and
deuterium atoms of 1.times.10.sup.20 cm.sup.-3 or more to
1.times.10.sup.22 cm.sup.-3 or less, and a density of bonds between
oxygen and hydrogen except bonds between excess oxygen (O.sub.EX)
and hydrogen in the amorphous oxide semiconductor being
1.times.10.sup.18 cm.sup.-3 or less.
Inventors: |
Hayashi; Ryo; (Yokohama-shi,
JP) ; Omura; Hideyuki; (Tokyo, JP) ; Kumomi;
Hideya; (Tokyo, JP) ; Shigesato; Yuzo;
(Sagamihara-shi, JP) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
1290 Avenue of the Americas
NEW YORK
NY
10104-3800
US
|
Assignee: |
CANON KABUSHIKI KAISHA
Tokyo
JP
|
Family ID: |
41426348 |
Appl. No.: |
12/534436 |
Filed: |
August 3, 2009 |
Current U.S.
Class: |
257/43 ; 257/52;
257/57; 257/59; 257/E21.414; 257/E29.068; 257/E29.291; 257/E33.053;
438/104; 438/158 |
Current CPC
Class: |
H01L 29/7869 20130101;
H01L 29/78663 20130101 |
Class at
Publication: |
257/43 ; 257/57;
257/59; 438/104; 257/52; 438/158; 257/E33.053; 257/E21.414;
257/E29.068; 257/E29.291 |
International
Class: |
H01L 33/00 20060101
H01L033/00; H01L 29/12 20060101 H01L029/12; H01L 29/786 20060101
H01L029/786; H01L 21/20 20060101 H01L021/20 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 28, 2008 |
JP |
2008-219888 |
Claims
1. An amorphous oxide semiconductor containing hydrogen and at
least one element of indium (In) and zinc (Zn), wherein: the
amorphous oxide semiconductor contains one of hydrogen atoms and
deuterium atoms of 1.times.10.sup.20cm.sup.-3 or more to
1.times.10.sup.22 cm.sup.-3 or less; and a density of bonds between
oxygen and hydrogen except bonds between excess oxygen (O.sub.EX)
and hydrogen in the amorphous oxide semiconductor is
1.times.10.sup.18 cm.sup.-3 or less.
2. A thin film transistor comprising a channel layer, a gate
insulating layer, a source electrode, a drain electrode, and a gate
electrode, wherein the channel layer comprises the amorphous oxide
semiconductor according to claim 1.
3. The thin film transistor according to claim 2, wherein an
electrical resistivity of the amorphous oxide semiconductor is more
than 10.OMEGA. and less than 1.times.10.sup.6.OMEGA..
4. The thin film transistor according to claim 2, wherein the
amorphous oxide semiconductor further comprises at least one of
gallium (Ga) and tin (Sn).
5. A display apparatus comprising a display device and a thin film
transistor, the display device including an electrode connected to
one of a source electrode and a drain electrode of the thin film
transistor on a substrate, wherein the thin film transistor
comprises a thin film transistor according to claim 2.
6. The display apparatus according to claim 5, wherein the display
device comprises an electroluminescent device.
7. The display apparatus according to claim 5, wherein the display
device comprises a liquid crystal cell.
8. The display apparatus according to claim 5, wherein a plurality
of the display devices and a plurality of the thin film transistors
are disposed two-dimensionally on the substrate.
9. A method of manufacturing a thin film transistor comprising a
substrate, a channel layer, a gate insulating layer, a source
electrode, a drain electrode, and a gate electrode, the channel
layer comprising an amorphous oxide semiconductor containing
hydrogen and at least one element of indium (In) and zinc (Zn), the
method comprising: forming the channel layer by sputtering using a
film forming gas containing water vapor; and carrying out thermal
treatment at 150.degree. C. or higher to 500.degree. C. or lower
after the channel layer is formed.
10. The method of manufacturing a thin film transistor according to
claim 9, wherein a partial pressure of the introduced water vapor
in the film forming gas is 8.times.10.sup.-4 Pa or higher.
11. A method of manufacturing a thin film transistor comprising a
substrate, a channel layer, a gate insulating layer, a source
electrode, a drain electrode, and a gate electrode, the channel
layer comprising an amorphous oxide semiconductor containing
hydrogen and at least one element of indium (In) and zinc (Zn), the
method comprising: forming the channel layer by applying a
solution; and carrying out thermal treatment at 500.degree. C. or
lower after the channel layer is formed.
12. A method of manufacturing a thin film transistor comprising a
substrate, a channel layer, a gate insulating layer, a source
electrode, a drain electrode, and a gate electrode, the channel
layer comprising an amorphous oxide semiconductor containing
hydrogen and at least one element of indium (In) and zinc (Zn), the
method comprising: forming the channel layer by electrodeposition;
and carrying out thermal treatment at 500.degree. C. or lower after
the channel layer is formed.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an amorphous oxide
semiconductor, a thin film transistor using the amorphous oxide
semiconductor film, and a method of manufacturing the thin film
transistor.
[0003] 2. Description of the Related Art
[0004] Recently, semiconductor devices using metal oxide
semiconductor thin films have attracted attention. The thin films
are characterized by being able to be formed at low temperatures,
and having a large optical band gap so as to be transparent to
visible light. Thus, a flexible and transparent thin film
transistor (TFT) or the like may be formed on plastic substrates,
film substrates, and the like (U.S. Pat. No. 6,727,522).
[0005] Conventionally, an oxide semiconductor film used as a TFT
active layer is, in order to control the electrical characteristics
of the film, generally formed in an atmosphere with oxygen gas
introduced thereinto. For example, U.S. Patent Application
Publication No. 2007/0194379 discloses a method of forming a thin
film transistor (TFT) in which an n-type oxide semiconductor
containing indium gallium zinc oxide (In--Ga--Zn--O) is used as a
channel layer and indium tin oxide (ITO) is used as source and
drain electrodes. In the film forming method described in U.S.
Patent Application Publication No. 2007/0194379, by controlling the
partial pressure of oxygen in an atmosphere in which the
In--Ga--Zn--O film is formed, carrier density is controlled,
thereby obtaining a high carrier mobility.
[0006] Further, Japanese Patent Application Laid-Open No.
2007-073697 discloses a technology of including water vapor in an
atmosphere gas in sputtering as a method of manufacturing a high
performance thin film transistor in which the above-mentioned oxide
semiconductor film is used as a channel layer. Further, U.S. Patent
Application Publication No. 2009/0045397 and Japanese Patent
Application Laid-Open No. 2007-194594 disclose technologies of
controlling the carrier density by introducing hydrogen into an
oxide semiconductor used as a channel layer of a thin film
transistor.
[0007] However, in a conventional oxide semiconductor film, even
when the carrier density is controlled by introducing hydrogen as
disclosed in U.S. Patent Application Publication No. 2009/0045397
and Japanese Patent Application Laid-Open No. 2007-194594, the
amount of hydrogen in the oxide semiconductor is orders of
magnitude greater than the carrier density. In other words, there
is a problem that it is impossible to control the carrier density
only by the amount of hydrogen in the film. Further, the inventors
of the present invention have studied formation of amorphous oxide
semiconductors including an amorphous In--Ga--Zn--O-based
semiconductor by sputtering to find that the amorphous oxide
semiconductors are very prone to take in hydrogen. For example, it
has been found that, even when the back pressure of an oxide
semiconductor sputtering apparatus is set to 2.times.10.sup.-4 Pa
or lower, there is a case in which hydrogen of 1.times.10.sup.20
cm.sup.-3 or more is contained. These studies have revealed that it
is difficult to form an amorphous oxide semiconductor containing
hydrogen of 1.times.10.sup.20 cm.sup.-3 or more at room temperature
at low cost without pretreatment such as thermal treatment and to
make the resistivity thereof appropriate for an amorphous oxide
thin film transistor.
SUMMARY OF THE INVENTION
[0008] The present invention has been made in view of the
above-mentioned problem, and an object of the present invention is
to provide an amorphous oxide thin film transistor having excellent
transistor characteristics.
[0009] According to the present invention, there is provided an
amorphous oxide semiconductor containing hydrogen and at least one
element of indium (In) and zinc (Zn), in which: the amorphous oxide
semiconductor contains one of hydrogen atoms and deuterium atoms of
1.times.10.sup.20 cm.sup.-3 or more to 1.times.10.sup.22 cm.sup.-3
or less; and a density of bonds between oxygen and hydrogen except
bonds (O.sub.EX--H bond and H--O.sub.EX--H bond) between excess
oxygen (O.sub.EX) (here, the excess oxygen means oxygen in excess
in a micro region when a size of several atoms constituting a part
of the amorphous oxide semiconductor) and hydrogen in the amorphous
oxide semiconductor is 1.times.10.sup.18 cm.sup.-3 or less.
[0010] According to the present invention, there is also provided a
display apparatus including a display device and a thin film
transistor, the display device including an electrode connected to
one of a source electrode and a drain electrode of the thin film
transistor on a substrate, in which the thin film transistor is the
thin film transistor described above.
[0011] According to the present invention, there is also provided a
method of manufacturing a thin film transistor including at least a
substrate, a channel layer, a gate insulating layer, a source
electrode, a drain electrode, and a gate electrode, the channel
layer including an amorphous oxide semiconductor containing
hydrogen and at least one element of indium (In) and zinc (Zn), the
method including: forming the channel layer by sputtering using a
film forming gas containing water vapor; and carrying out thermal
treatment at 150.degree. C. or higher to 500.degree. C. or lower
after the channel layer is formed.
[0012] According to the present invention, there is also provided a
method of manufacturing a thin film transistor including at least a
substrate, a channel layer, a gate insulating layer, a source
electrode, a drain electrode, and a gate electrode, the channel
layer including an amorphous oxide semiconductor containing
hydrogen and at least one element of indium (In) and zinc (Zn), the
method including: forming the channel layer by applying a solution;
and carrying out thermal treatment at 500.degree. C. or lower after
the channel layer is formed.
[0013] According to the present invention, there is also provided a
method of manufacturing a thin film transistor including at least a
substrate, a channel layer, a gate insulating layer, a source
electrode, a drain electrode, and a gate electrode, the channel
layer including an amorphous oxide semiconductor containing
hydrogen and at least one element of indium (In) and zinc (Zn), the
method including: forming the channel layer by electrodeposition;
and carrying out thermal treatment at 500.degree. C. or lower after
the channel layer is formed.
[0014] The present invention is able to provide at low cost a TFT
device in which an amorphous oxide semiconductor is used as a
channel layer thereof and which may precisely control the carrier
density and has satisfactory transistor characteristics.
[0015] Further features of the present invention become apparent
from the following description of exemplary embodiments with
reference to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIGS. 1A, 1B, 1C, 1D, 1E, and 1F illustrate atomic
configurations obtained by calculating structural relaxation of an
amorphous InGaZnO.sub.4 (a-IGZO) structural model according to the
present invention.
[0017] FIGS. 2A, 2B, 2C, 2D, 2E, 2F, and 2G illustrate density of
states (DOS) obtained by calculation with regard to the models
illustrated in FIGS. 1A to 1F using cut-off energy of 400 eV and a
4.times.5.times.6 Monkhost-Pack special k-point mesh.
[0018] FIG. 3 is a graph illustrating a relationship between
carrier density, Hall mobility, and resistivity and partial
pressure of water vapor when a film is formed by sputtering,
obtained by measuring a Hall effect of a-IGZO.
[0019] FIG. 4 is a schematic sectional view of a thin film
transistor according to an embodiment of the present invention.
[0020] FIG. 5 is a graph illustrating transfer characteristics of
the thin film transistor according to the embodiment of the present
invention.
[0021] FIG. 6 is a sectional view of an example of a display
apparatus according to another embodiment of the present
invention.
[0022] FIG. 7 is a sectional view of another example of the display
apparatus according to the another embodiment of the present
invention.
[0023] FIG. 8 illustrates a structure of a display apparatus in
which pixels including organic electroluminescent (EL) devices and
thin film transistors are disposed two-dimensionally according to
the another embodiment of the present invention.
[0024] FIG. 9 is a schematic sectional view illustrating a thin
film transistor according to another embodiment of the present
invention.
[0025] FIG. 10 is a graph illustrating a relationship between an
amount of hydrogen in an amorphous oxide semiconductor film
prepared in Example 1 and a partial pressure of water vapor in a
sputtering gas.
[0026] FIG. 11 is a graph illustrating transfer characteristics of
a thin film transistor prepared in Example 2.
[0027] FIG. 12 is a schematic sectional view of a thin film
transistor prepared in Example 4.
DESCRIPTION OF THE EMBODIMENTS
[0028] Embodiments of the present invention are described below
with reference to the attached drawings.
[0029] First, a relationship between hydrogen and carrier density
with regard to amorphous In--Ga--Zn--O on which the inventors of
the present invention energetically conducted research and
development is described.
[0030] Now it is known that, by injecting hydrogen ions into an
amorphous In--Ga--Zn--O thin film used in an amorphous oxide
semiconductor TFT, the electrical conductivity of the thin film is
enhanced and hydrogen behaves as a donor in the film (see U.S.
Patent Application Publication No. 2009/0045397). On the other
hand, in an amorphous In--Ga--Zn--O thin film formed by sputtering
or the like, even when ion implantation or the like is not carried
out, hydrogen atoms of up to about 1.times.10.sup.20 cm.sup.-3 are
contained. This comes from residual gas of molecular species
containing hydrogen such as H.sub.2 and H.sub.2O which exist in a
chamber in which the film is formed. The amorphous In--Ga--Zn--O
thin film formed in this way has a carrier electron density of
about 1.times.10.sup.18 cm.sup.-3 or less depending on the film
forming conditions. The difference between the concentration of
hydrogen atoms and the carrier electron density in the film is
about 1.times.10.sup.2 cm.sup.-3 or more, and thus, it is thought
that most of the hydrogen atoms existing in the film do not
function as a donor.
[0031] Reviews by the inventors of the present invention by
calculating the electronic structure revealed that, depending on
the bonding state between oxygen and hydrogen existing in the film,
hydrogen which did not function as a donor existed, which is
described in detail below. It is to be noted that, in the present
invention, not only hydrogen atoms but also deuterium atoms are
regarded as hydrogen involved in the carrier density.
[0032] (Calculation Model)
[0033] An amorphous InGaZnO.sub.4 (a-IGZO) structural model was
obtained as in the following. A crystalline InGaZnO.sub.4 cell
model containing 2,016 atoms was melted by classical molecular
dynamics (MD) for 20 psec. at 8,000 K with a time step of 2 fsec.
After rapid cooling from 8,000 K to 12 K at a rate of 125 K/psec.,
a classical MD simulation was performed for 100 psec. at 1 K. In
this way, a stable structure of amorphous a-IGZO in the classical
MD simulation was obtained. A cell containing 84 atoms which could
be performed by first principles calculation was cut out from this
model and was once again melted and rapidly cooled by the classical
MD simulation under the above-mentioned conditions to obtain an
84-atom a-IGZO model. Buckingham potential was used in these
classical MD simulations. Parameters of the potential were
determined such that experimental values of the first nearest
neighbor distances and mass densities of a-IGZO films were
reproduced with errors of 2% or less and 10% or less,
respectively.
[0034] Structural relaxation was calculated using first principles
band calculation based on a plane-wave basis set and a projected
argument wave method with the obtained 84-atom a-IGZO model as a
unit cell to obtain a stable structure of an a-IGZO model with no
impurity contained therein (hereinafter referred to as "pure
a-IGZO"). The structural relaxation calculated using first
principles band calculation which is described below used a
plane-wave basis set with a cut-off energy of 400 eV, and a
4.times.4.times.1 Monkhost-Pack special k-point mesh under
conditions such that the charge in the unit cell was neutral.
[0035] Structural relaxation was calculated with regard to a-IGZO
having a hydrogen atom added thereto (hereinafter referred to as
"a-IGZO+H") and a-IGZO having an oxygen atom O.sub.EX as excess
oxygen added thereto (hereinafter referred to as "a-IGZO+O") as
a-IGZO structural models containing an impurity. These atoms were
located at a location which is about 0.15 nm from oxygen O(A)
illustrated in the structural models of a-IGZO+H and a-IGZO+O of
FIGS. 1A and 1B, respectively.
[0036] Then, structural relaxation was calculated with regard to
the a-IGZO+O model after the structural relaxation, which has a
hydrogen atom or two hydrogen atoms further added thereto at a
location far from the added oxygen atom O.sub.EX (a-IGZO+OH or
a-IGZO+OH.sub.2). Further, structural relaxation was calculated
with regard to the a-IGZO+O model after the structural relaxation,
which has a hydrogen atom or two hydrogen atoms further added
thereto at a location near the added oxygen atom O.sub.EX
(a-IGZO+O.sub.EXH or a-IGZO+O.sub.EXH.sub.2).
[0037] With regard to the structural models obtained by calculating
the above-mentioned structural relaxation, density of states (DOS)
was calculated. The structural models mean a-IGZO, a-IGZO+H,
a-IGZO+O, a-IGZO+OH, a-IGZO+OH.sub.2, a-IGZO+O.sub.EXH, and
a-IGZO+O.sub.EXH.sub.2. It is to be noted that, in calculating the
density of states (DOS), cut-off energy of 400 eV and a
4.times.5.times.6 Monkhost-Pack special k-point mesh were used.
[0038] (Results of Calculation)
[0039] FIGS. 1A to 1F illustrate relaxed atomic configurations of
the above-mentioned models obtained by structural relaxation. In
a-IGZO+H (FIG. 1A), the hydrogen added as an impurity forms a bond
with oxygen existing in the pure a-IGZO model (O(A) in the figure).
In a-IGZO+O (FIG. 1B), the oxygen O.sub.EX added as excess oxygen
forms an O--O.sub.EX bond with oxygen existing nearby in the pure
a-IGZO model (O(A) in the figure). In a-IGZO+OH (FIG. 1C) and
a-IGZO+OH.sub.2 (FIG. 1D), the excess oxygen maintains the
O--O.sub.EX bond, and the added hydrogen forms a bond with oxygen
existing nearby in the pure a-IGZO model. On the other hand, in
a-IGZO+O.sub.EXH (FIG. 1E) and a-IGZO+O.sub.EXH.sub.2 (FIG. 1F),
the hydrogen located near the excess oxygen breaks the O--O.sub.EX
bond, and an O.sub.EX--H--O bond or an H--O.sub.EX--H bond is
formed between the excess oxygen and the hydrogen. In particular,
from FIG. 1F illustrating a-IGZO+O.sub.EXH.sub.2, it may be seen
that the structure of H--O.sub.EX--H is similar to that of
water.
[0040] FIGS. 2A to 2G illustrate DOS obtained with regard to the
above-mentioned models. Further, for comparison purposes, DOS of
the pure a-IGZO is illustrated (FIG. 2A). In these figures, the top
energy of the valence band of pure a-IGZO is 0 eV. A solid line in
the figures designates the Fermi level. In the DOS of a-IGZO+H
(FIG. 2B), the Fermi level is in the conduction band. This means
that electrons--as carriers are doped in the conduction band, which
is coincident with the fact that hydrogen behaves as a donor. In
the DOS of a-IGZO+O (FIG. 2C), the Fermi level does not exist in
the conduction band. Further, a level peak which comes from the
O--O bond is observed above the valence band. Because the level is
completely occupied by electrons, the excess oxygen does not affect
the electrical characteristics of an n-type TFT. In the DOS of
a-IGZO+OH (FIG. 2D) and a-IGZO+OH.sub.2 (FIG. 2E) in which the
a-IGZO+O structural model has hydrogen added thereto at a location
far from the excess oxygen, a peak which comes from the O--O.sub.EX
bond is observed above the valence band, and the Fermi level is in
the conduction band. The excess oxygen and the hydrogen exhibit
their respective characteristics independently of each other, which
shows that there is a case in which, even when excess oxygen
exists, the excess oxygen does not function as carrier killers. On
the other hand, in the DOS of a-IGZO+O.sub.EXH (FIG. 2F) in which
the a-IGZO+O structural model has hydrogen added thereto at a
location near the excess oxygen, a steep peak of the O--H--O.sub.EX
bond which comes from the excess oxygen and the hydrogen is
observed in the band gap. Therefore, judging from the location of
the Fermi level, it may be seen that the level is an incompletely
occupied level. Thus, the level acts as a trap for capturing
carrier electrons. In the DOS of a-IGZO+O.sub.EXH.sub.2 (FIG. 2G),
the level in the gap observed in a-IGZO+O.sub.EXH (FIG. 2F)
disappears, the Fermi level does not exist in the conduction band,
and the DOS is similar to that of pure a-IGZO. Therefore, in this
case, the hydrogen cannot be an impurity which greatly affects the
electrical characteristics of the TFT.
[0041] From the above, the reason for the fact that, while the
experimental fact shows that hydrogen in an amorphous oxide
semiconductor functions as a donor, the concentration of hydrogen
atoms existing in the film is not in good agreement with the
carrier electron density is thought to be as follows. A case in
which hydrogen is introduced by ion implantation into an amorphous
oxide semiconductor thin film corresponds to the above-mentioned
case of a-IGZO+H, and the hydrogen is ionized to function as a
donor. On the other hand, it is suggested that, in a thin film
formed with the partial pressure of oxygen or the partial pressure
of water being controlled, most hydrogen existing in the film does
not function as a donor. From the above-mentioned calculation, when
excess oxygen having the composition ratio different from its
stoichiometric composition ratio in a-IGZO and hydrogen form a
chemical bond of O--H--O.sub.EX or O.sub.EX--H.sub.2, the hydrogen
does not function as a donor. In this case, O--H--O.sub.EX
functions as a carrier trap while O.sub.EX--H.sub.2 does not affect
the electrical characteristics of the TFT. Therefore, it is thought
that, in a formed film, because a large ratio of existing hydrogen
exists in a bonding state of O--H--O.sub.EX or O.sub.EX--H.sub.2, a
carrier electron density which attains a normally off TFT device is
maintained.
[0042] The excess oxygen as used herein does not mean that the
oxygen is excessive compared with its stoichiometric composition
ratio in the entire amorphous oxide semiconductor, but means that
the oxygen is excessive in a minute region with a specific number
of atoms in a part of the amorphous oxide semiconductor as a unit
size. Therefore, even when the oxygen exists according to its
stoichiometric composition ratio in the entire amorphous oxide
semiconductor, if the amount of oxygen deficiency and the amount of
excess oxygen are to the same extent, there is the excess oxygen as
used herein.
[0043] Specifically, the existence of excess oxygen means that,
though oxygen is to be bonded with a metallic element M (where M is
In, Zn, or Ga) and the bonding state is to be M-O-M, the bonding
state is actually M-O--O-M including O--O. This bonding state of
oxygen is expressed as O--O.sub.EX bond. When hydrogen is bonded to
this O--O.sub.EX bond, the bonding state is expressed as
O.sub.EX--H or H--O.sub.EX--H.
[0044] An O--H bond as used herein means the a-IGZO+OH bond
described above. Further, an O.sub.EX--H bond formed by excess
oxygen compared with its stoichiometric composition ratio in
relation to a metallic element and by hydrogen means the
a-IGZO+O.sub.EXH bond described above having the structure in which
hydrogen is inserted into the O--O.sub.EX bond of the excess
oxygen. Further, an H--O.sub.EX--H bond formed by excess oxygen and
hydrogen means the a-IGZO+O.sub.EXH.sub.2 bond described above.
[0045] As described above, it has been found that hydrogen in an
amorphous oxide semiconductor does not function as a donor when
oxygen near the hydrogen is locally excessive. Specifically, in an
amorphous oxide semiconductor containing excess hydrogen in
relation to the carrier density, the number of the a-IGZO+OH bonds
which are the source of the carriers determines the final carrier
density of the amorphous oxide semiconductor. In other words, the
density of the O--H bonds is the carrier density.
[0046] When a large amount of (1.times.10.sup.20 cm.sup.-3 or more)
hydrogen atoms are contained in the amorphous oxide semiconductor,
it is important that the ratio of the number of the excess oxygen
atoms to the number of the hydrogen atoms is 1:2 or more when the
excess oxygen atoms and the hydrogen atoms are taken in the
amorphous oxide semiconductor. In this way, 5.times.10.sup.19
cm.sup.-3 or more excess oxygen atoms may be contained and the
carrier density may be 1.times.10.sup.18 cm.sup.-3, which is
sufficient to function as a channel layer semiconductor of a TFT.
When the number of the hydrogen atoms is less than
1.times.10.sup.20 cm.sup.-3, because the carrier density due to a
source of carriers other than the hydrogen, such as oxygen
deficiency, competes with the carrier density due to the O--H bond
(the difference in density becomes smaller), there is a case in
which the relationship according to the present invention does not
hold (the density of the O--H bond falls out of the range according
to the present invention), which is not preferable.
[0047] Further, when a large amount of (1.times.10.sup.21 cm.sup.-3
or more) hydrogen atoms are contained in the amorphous oxide
semiconductor, the concentration of O--H--O.sub.EX which functions
as a carrier trap increases. In order to suppress the increase of
the trap, it is more important not to add oxygen but to add only
water vapor to Ar gas as the sputtering gas. As an example, the
sputtering gas may be formed by adding only water vapor to Ar gas.
FIG. 3 illustrates the dependence of the carrier density, the Hall
mobility, and the resistivity on the partial pressure of water
vapor when a film is formed by sputtering, obtained by measuring
the Hall effect of a-IGZO prepared according to this embodiment.
Depending on the film forming conditions by sputtering such as the
gas pressure and the density of the applied power, by introducing a
partial pressure of water vapor of 1.times.10.sup.-2 Pa or higher,
the resistivity of a-IGZO may be increased. Further, the carrier
density may be made to be 1.times.10.sup.18 cm.sup.-3 or less. The
upper limit of the amount of the hydrogen is 1.times.10.sup.22
cm.sup.-3. The upper limit is set because it is difficult to supply
with stability more hydrogen by water vapor to the amorphous oxide
semiconductor thin film. Further, because the density of
O--H--O.sub.EX which functions as a carrier trap becomes higher, it
is impossible to obtain electrical characteristics which are
necessary for the TFT to operate. For example, the threshold value
of the TFT becomes extremely high.
[0048] FIG. 4 is a schematic view of a structure of a TFT device
prepared according to this embodiment. The TFT device is formed by
providing on a substrate 10 a gate electrode 15, a gate insulating
film 14, a source electrode 12 and a drain electrode 11, a channel
layer 13, and a protective layer 16 in this order.
[0049] The structure of the semiconductor device applicable to the
present invention is not limited to the TFT of the bottom gate
structure as described above. For example, the TFT may have a
reverse stagger structure in which a gate insulating film and a
semiconductor channel layer are provided in this order on a gate
electrode and then a source electrode and a drain electrode are
formed thereon or may have a stagger structure (top gate structure)
which is an upside-down reverse stagger structure.
[0050] According to findings by the inventors of the present
invention, it is preferable that a thin film transistor in which an
amorphous oxide semiconductor layer containing hydrogen and at
least one element of In and Zn is used as a channel layer have,
depending on the composition, the following characteristics: when a
semi-insulating oxide film having an electrical resistivity of more
than about 10 .OMEGA.cm and less than about 1.times.10.sup.6
.OMEGA.cm is used, satisfactory TFT characteristics may be
obtained. For example, when the electrical resistivity is 10
.OMEGA.cm or less, it is impossible to obtain a normally-off
transistor or a large on/off ratio. In extreme cases, even when
gate voltage is applied, current between the source and drain
electrodes is not turned on/off, and the transistor does not
operate. On the other hand, when the electrical resistivity is
1.times.10.sup.6 .OMEGA.cm or more, it is impossible to obtain a
large on-current. In extreme cases, even when gate voltage is
applied, current between the source and drain electrodes is not
turned on/off, and the transistor does not operate.
[0051] Normally, the electrical resistivity and the carrier density
of an oxide are controlled by the partial pressure of oxygen which
is introduced when the film is formed. More specifically, by
controlling the partial pressure of the oxygen, mainly the amount
of oxygen deficiency in the thin film is controlled, by which the
electron carrier density is controlled. However, according to the
present invention, the electron carrier density is controlled by
controlling only the partial pressure of water vapor illustrated in
FIG. 3.
[0052] A method of forming the channel layer according to the
present invention is described in detail below.
[0053] First, the substrate 10 made of glass or the like is
prepared. By a vapor phase method such as DC sputtering, RF
sputtering, pulsed-laser deposition, atomic layer deposition, or
electron beam deposition, a combination thereof, or the like, the
amorphous oxide semiconductor film is formed. Here, the film is
formed under such a condition that the electrical resistivity of
the amorphous oxide semiconductor film is higher than a resistivity
with which satisfactory characteristics for a TFT channel layer are
obtained. This is accomplished basically by, depending on the
composition of the amorphous oxide semiconductor film and the film
forming apparatus, setting the partial pressure of the introduced
water vapor in a range which is 8.times.10.sup.-4 Pa or higher. In
particular, when the partial pressure of the introduced water vapor
is 1.times.10.sup.-2 Pa or higher, this may be accomplished easily.
When the film is formed using a vacuum apparatus, the upper limit
of the partial pressure of the introduced water vapor is the
pressure of the film forming gas. In order to prevent decreased
density of the film and decreased speed of film formation due to
polymerization in a vapor phase, the partial pressure of the
introduced water vapor is desirably about 10 Pa or lower. In order
to strictly control the resistivity, water vapor and oxygen the
amount of which is small compared with that of the water vapor may
be simultaneously introduced and controlled.
[0054] The partial pressure of the introduced water vapor as used
herein means the partial pressure of water vapor which is
intentionally introduced into the film forming apparatus by a flow
rate controller. Water vapor which is inevitably released from an
inner wall of the film forming apparatus or the like, water vapor
which enters from the outside because the film forming apparatus
leaks, and water vapor released from a target greatly vary
depending on the history of the film formation, and thus, are very
difficult to control. It is technically possible to make the back
pressure of the vacuum film forming apparatus an ultrahigh vacuum
of 1.times.10.sup.-8 Pa or lower and to control the concentration
of hydrogen in the amorphous oxide to be less than the carrier
density. However, if this is done, a problem that the manufacturing
cost is increased arises including increased cost of the film
forming apparatus and a lengthened manufacturing tact time.
However, when the pressure of residual water vapor exceeds the
upper limit of the partial pressure of the introduced water vapor,
it is difficult to obtain the effect of the present invention, and
thus, it is preferable that the back pressure of the film forming
apparatus used in the present invention be 5.times.10.sup.-4 Pa or
lower. It is to be noted that the flow rate controller is, for
example, a mass flow controller.
[0055] Further, here, from the viewpoint of the performance of the
TFT device, it is preferable that the film be formed under such a
condition that the resistivity of the amorphous oxide semiconductor
film is 1.times.10.sup.2 .OMEGA.cm or more. It is to be noted that,
according to the present invention, the lower limit of the
resistivity after the metallic film is formed is, depending on the
composition and the film forming conditions of the oxide film,
1.times.10 .OMEGA.cm or more, for example.
[0056] After that, the prepared amorphous oxide semiconductor film
may be thermally treated. Here, the thermal treatment conditions
are set such that the amorphous oxide semiconductor film has a
resistivity with which satisfactory characteristics for a TFT
channel layer are obtained. In order to control the resistivity
uniformly in a short time, the thermal treatment may be carried out
with the temperature of the atmosphere being 150.degree. C. or
higher to 500.degree. C. or lower, preferably 200.degree. C. or
higher to 350.degree. C. or lower. Further, to use an oxidizing
atmosphere is effective from the viewpoint of uniformity, and thus,
this is also preferable.
[0057] When the thermal treatment is carried out, the following are
thought to happen: the hydrogen atoms are thermally diffused in the
amorphous oxide; the diffused hydrogen is bonded to O--H--O.sub.EX
which functions as a carrier trap to produce O.sub.EX--H.sub.2
which does not affect the electrical characteristics of the TFT;
and the carrier trap density is decreased.
[0058] A preferable method of forming the TFT at low cost is to
form an amorphous oxide semiconductor film by applying a solution.
For example, first, a solution of Zn(CH.sub.3COO).sub.22H.sub.2O
(available from Aldrich) and In(CH.sub.3COO).sub.3 (available from
Aldrich) dissolved in 2-methoxyethanol as a solvent is applied by
inkjet printing as the material. Then, thermal treatment is carried
out in the atmosphere at a temperature of 500.degree. C. or lower
to obtain an amorphous InZnO film. In order to sufficiently
volatilize the solvent, the thermal treatment may be carried out at
150.degree. C. or higher to 500.degree. C. or lower, preferably at
200.degree. C. or higher to 350.degree. C. or lower. The upper
limit of the temperature of the thermal treatment is restricted by
crystallization of the oxide semiconductor film. Here,
1.times.10.sup.20 cm.sup.-3 or more hydrogen atoms remain in the
amorphous oxide semiconductor film, and the number of M-OH bonds of
1.times.10.sup.18 cm.sup.-3 or less which materializes the carrier
density of the present invention may be materialized.
Electrodeposition may be employed as a method of forming the film
using another solvent. For example, with an aqueous solution
containing indium nitrate, gallium nitrate, zinc nitrate, and
dimethylamine-borane (DMAB) being used as the material, an
In--Ga--Zn--O-based amorphous oxide thin film may be formed on an
insulating substrate (for example, Corning 1737). After an initial
deposited layer is deposited without an electric field applied
thereto, an electric field may be applied using an aqueous solution
which does not contain dimethylamine-borane (DMAB) and using an
external power supply to form an amorphous oxide film by
electrodeposition. Here, the temperature of the aqueous solution is
60.degree. C. The amorphous oxide film formed in this way has
therein a large amount of (1.times.10.sup.20 cm.sup.-3 or more)
residual hydrogen atoms. By thermally treating the film at
500.degree. C. or lower, the number of M-OH bonds of
1.times.10.sup.18 cm.sup.-3 or less and the carrier density of
1.times.10.sup.18 cm.sup.-3 or less in the present invention may be
materialized. In this way, an amorphous oxide semiconductor film
which may operate as a TFT may be formed. In order to volatilize a
large amount of moisture contained in the film, the thermal
treatment may be carried out at 150.degree. C. or higher to
500.degree. C. or lower, preferably at 200.degree. C. or higher to
350.degree. C. or lower. The upper limit of the temperature of the
thermal treatment is restricted by crystallization of the oxide
semiconductor film.
[0059] Then, an oxide insulator protective film is formed by
sputtering in an atmosphere containing oxygen, by which damage to
the channel layer due to the formation of the protective film and
an effect of reduction may be cancelled out.
[0060] Components of the TFT structure are described in detail
below.
[0061] (Gate Insulating Layer)
[0062] In the present invention, it is desirable to use SiO.sub.2
for the gate insulating layer. Alternatively, it is also preferable
to use a material containing at least one kind of SiO.sub.2,
Y.sub.2O.sub.3, Al.sub.2O.sub.3, HfO.sub.2 and TiO.sub.2 for the
gate insulating layer. Any film in which these layers are laminated
may also be used.
[0063] As the film formation method for a gate insulating layer,
vapor phase methods such as sputtering, pulsed-laser deposition and
electron beam deposition may be used. However, the film formation
method is not limited to these methods.
[0064] (Electrode)
[0065] The materials for the source electrode, the drain electrode
and the gate electrode are not particularly constrained as long as
the materials enable satisfactory electrical conductance and
satisfactory electrical connection to the channel layer. For
example, usable are transparent conductive films formed of
In.sub.2O.sub.3:Sn or ZnO, and metal films formed of Mo, Au, Pt, Al
Ni, and Cu. In addition, for the purpose of improving adhesion, a
layer formed of Ti, Ni, Cr, and the like may be disposed between
the channel layer or the insulating layer and the electrodes.
[0066] (Substrate)
[0067] As the substrate, a glass substrate, a metal substrate, a
plastic substrate, a plastic film, and the like may be used,
depending on the thermal treatment conditions of the channel layer,
and the like.
[0068] (Channel Layer)
[0069] The channel layer is an amorphous oxide containing hydrogen
and at least one element of In and Zn.
[0070] As the film formation method for a channel layer, vapor
phase methods such as sputtering, pulsed-laser deposition and
electron beam deposition may be used. However, the film formation
method is not limited to these methods.
[0071] In order to ensure that a fixed amount of hydrogen is taken
in the amorphous oxide semiconductor, and thus, in order to prevent
water vapor from being adsorbed to an underlayer of the channel
layer or to a wall of the chamber of the vacuum apparatus before
the film formation is started, it is desirable that the channel
layer be formed at 80.degree. C. or higher.
[0072] It is desirable that the temperature of the thermal
treatment be equal to or lower than a glass transition temperature,
and, in the present invention, it is desirable that the temperature
of the thermal treatment be 150.degree. C. or higher to 500.degree.
C. or lower. The lower limit of the temperature of the thermal
treatment is 150.degree. C. because decomposition of In(OH).sub.3
which is a well-known material used when metallic indium is refined
therefrom begins at 150.degree. C. From the viewpoint of shortening
the thermal treatment time, it is preferable that the temperature
of the thermal treatment be 200.degree. C. or higher to 350.degree.
C. or lower.
[0073] Because the thermal treatment may be carried out by
utilizing the temperature at which the channel layer is formed, the
thermal treatment may be carried out simultaneously with the
formation of the channel layer. Also, the thermal treatment may be
carried out after the protective film is formed, or, may be carried
out after the TFT is completed.
[0074] (Protective Film)
[0075] As the protective film, a metal oxide film containing at
least one kind of metal element is used. Of metal oxides, it is
preferred to use, as the protective film, a substance containing at
least one of the following: SiO.sub.2, Al.sub.2O.sub.3,
Ga.sub.2O.sub.3, In.sub.2O.sub.3, MgO, CaO, SrO, BaO, ZnO,
Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, TiO.sub.2, ZrO.sub.2, HfO.sub.2,
CeO.sub.2, Li.sub.2O, Na.sub.2O, K.sub.2O, Rb.sub.2O,
Sc.sub.2O.sub.3, Y.sub.2O.sub.3, La.sub.2O.sub.3, Nd.sub.2O.sub.3,
Sm.sub.2O.sub.3, Gd.sub.2O.sub.3, Dy.sub.2O.sub.3, Er.sub.2O.sub.3
and Yb.sub.2O.sub.3.
[0076] Alternatively, silicon nitroxide (SiO.sub.xN.sub.y) may also
be used, in addition to these metal oxides.
[0077] As the method of forming the above-mentioned metal oxide or
SiO.sub.xN.sub.y as the protective film on the TFT, chemical vapor
deposition (CVD), sputtering, and the like may be used. When the
protective film is formed by sputtering, the film formation is
conducted during sputtering in an oxygen-containing atmosphere.
This is because a device, in which the protective film is formed,
for example, in an Ar gas atmosphere, is degraded in TFT
characteristics as compared to before formation of the protective
film. The cause for the degradation of the TFT characteristics is
conceivably the decrease in resistance of the channel layer by the
carrier generation due to the oxygen release from the interface of
the channel layer during formation of the protective film.
Consequently, the film formation is required to be conducted in an
oxygen-containing atmosphere during sputtering the protective film.
The oxygen content in the total sputtering gas is desirably 10% to
80%.
[0078] (TFT Characteristics)
[0079] FIG. 5 illustrates the typical transfer characteristic
(Vg-Id characteristic) of the TFT of the present invention. When a
voltage Vd of 12 V is applied between the source and drain
electrodes, by sweeping the gate voltage Vg between -20 V and 20 V,
the current Id between the source and drain electrodes may be
controlled (turned on and off).
[0080] In particular, when the present invention is applied to a
TFT using, as a channel layer, an amorphous oxide having a high
carrier mobility originally due to no grain boundary scattering and
excellent interface characteristics, a TFT having a high
field-effect mobility and excellent characteristics may be
actualized. In this case, the amorphous phase is stabilized by
incorporating at least one element of Ga and Sn in the oxide film.
In addition, from the viewpoint of the stabilization of the
amorphous phase, it is conceivable that the temperature of the
oxidizing atmosphere at the time of the thermal treatment is
preferably set at 500.degree. C. or lower.
[0081] Here, the state of being amorphous may be identified by the
observation that no distinct diffraction peaks are detected (in
other words, halo patterns are observed) when X-ray is diffracted
to a thin film, as a measurement target, with a low incidence angle
of approximately 0.5 degrees. It should be noted that when the
above-mentioned materials are used for the channel layer of a thin
film transistor, the present invention does not exclude the case
where the channel layer contains microcrystalline-state constituent
materials.
[0082] By connecting an electrode of a display device such as an
organic or inorganic electroluminescent (EL) device or a liquid
crystal device to a drain which is an output terminal of the
above-mentioned thin film transistor, a display apparatus may be
formed. Specific examples of display apparatus structures are
described below with reference to sectional views of display
apparatus.
[0083] FIG. 6 is a sectional view of an exemplary display apparatus
as another embodiment of the present invention. A TFT is formed on
a substrate 611. The TFT includes a gate electrode 612, a gate
insulating film 613, an amorphous oxide semiconductor film 614, a
protective layer 615, a source (drain) electrode 616, and a drain
(source) electrode 617.
[0084] An electrode 618 is connected to the drain (source)
electrode 617 via an interlayer insulating film 619. The electrode
618 is in contact with an emission layer 620. The emission layer
620 is in contact with an electrode 621.
[0085] With such a structure, current injected into the emission
layer 620 may be controlled by a value of current which passes from
the source (drain) electrode 616 to the drain (source) electrode
617 via a channel formed in the amorphous oxide semiconductor film
614.
[0086] Therefore, the current may be controlled by the voltage at
the gate electrode 612 of the TFT. Here, the electrode 618, the
emission layer 620, and the electrode 621 form an inorganic or
organic electroluminescent device.
[0087] FIG. 7 is a sectional view of another exemplary display
apparatus as the another embodiment of the present invention. A
drain (source) electrode 717 is extended so as to also serve as an
electrode 718. An electrode 723 and opposite electrode 718 may be
structured to apply voltage to a liquid crystal cell or an
electrophoretic particle cell 721 sandwiched between high
resistance films 720 and 722. FIG. 7 also illustrates a substrate
711, a gate insulating film 713, a protective layer 715, and an
interlayer insulating film 719.
[0088] The liquid crystal cell or electrophoretic particle cell
721, the high resistance films 720 and 722, the electrode 718, and
the electrode 723 form a display device.
[0089] Voltage applied to the display device may be controlled by a
value of current which passes from a source electrode 716 to the
drain electrode 717 via a channel formed in an amorphous oxide
semiconductor film 714.
[0090] Therefore, the voltage may be controlled by the voltage at a
gate electrode 712 of the TFT. Here, when a display medium of the
display device is a capsule having fluid and particles encapsulated
in an insulating film thereof, the high resistance films 720 and
722 may be eliminated.
[0091] The two example TFTs have been described above as TFTs
having a bottom gate reverse stagger structure, but the present
invention is not limited to such a structure.
[0092] For example, as long as the connection between the drain
electrode which is an output terminal of the TFT and the display
device is topologically the same, other structures such as a
coplanar structure are also possible.
[0093] Further, in the two example TFTs described above, the
electrodes in a pair for driving the display device are provided so
as to be in parallel with the substrate, but the present invention
is not limited to such a structure.
[0094] For example, as long as the connection between the drain
electrode which is an output terminal of the TFT and the display
device is topologically the same, one or both of the electrodes may
be provided so as to be perpendicular to the substrate.
[0095] Still further, with regard to the two example TFTs described
above, only one TFT is illustrated to be connected to the display
device, but the present invention is not limited to such a
structure. For example, the TFT illustrated in the figures may be
further connected to another TFT according to the present
invention, as long as the TFT illustrated in the figures is at the
last stage of a circuit including these TFTs.
[0096] Here, when the electrodes in a pair for driving the display
device are provided so as to be in parallel with the substrate, if
the display device is a reflective display device such as an EL
device or a reflective liquid crystal device, any one of the
electrodes is required to be transparent with respect to the
wavelength of emitted light or of reflected light.
[0097] If the display device is a transmissive display device such
as a transmissive liquid crystal device, both of the electrodes are
required to be transparent with respect to transmitted light.
[0098] Further, in the TFT according to this embodiment, all the
components may be transparent so that a transparent display device
may be formed.
[0099] Further, such a display device may be provided on a
substrate which has low heat resistance, such as a lightweight,
flexible, and transparent plastic resin substrate.
[0100] Next, a display apparatus in which a plurality of pixels
including EL devices (here, organic EL devices) and thin film
transistors are disposed two-dimensionally is described with
reference to FIG. 8.
[0101] In FIG. 8, a transistor 801 drives an organic EL layer 804.
A transistor 802 selects a pixel. A capacitor 803 maintains a
selected state, holds charge between a common electrode line 807
and a source of the transistor 802, and holds a signal at a gate of
the transistor 801. A pixel is selected through a scanning
electrode line 805 and a signal electrode line 806.
[0102] More specifically, an image signal is applied as a pulse
signal from a driver circuit (not shown) via the scanning electrode
line 805 to a gate electrode. At the same time, a signal is applied
also as a pulse signal from another driver circuit (not shown) via
the signal electrode line 806 to the transistor 802 to select a
pixel. Here, the transistor 802 is turned on and charge is stored
in the capacitor 803 between the signal electrode line 806 and the
source of the transistor 802.
[0103] This makes the gate of the transistor 801 held at a desired
voltage and the transistor 801 is turned on. This state is
maintained until the next signal is received.
[0104] During a time period in which the transistor 801 is on,
voltage and current continue to be supplied to the organic EL layer
804 and light emission is maintained.
[0105] Although the structure illustrated in FIG. 8 has two
transistors and one capacitor per pixel, more transistors and the
like may be incorporated in order to improve the performance.
[0106] What is essential is that, by using an In--Ga--Zn--O-based
TFT which is transparent and may be formed at a low temperature for
the transistor part, an effective EL device may be obtained.
[0107] Although the present invention is further described below
with reference to examples, the present invention is not limited
thereto.
Example 1
[0108] In this example, an embodiment of a TFT device of the
present invention is described.
[0109] First, an In--Ga--Zn--O film was formed on a glass substrate
as an amorphous oxide semiconductor. The In--Ga--Zn--O film was
formed in an argon atmosphere by DC sputtering film formation.
[0110] As a target (material source), a 3-inch sized sintered body
having a composition of InGaZnO.sub.4 was used, and the applied RF
power was 50 W. The distance between the target and the substrate
was 60 mm. The In--Ga--Zn--O film was formed in a mixed atmosphere
at 5.0.times.10.sup.-1 Pa of argon and water vapor. The partial
pressure of the introduced water vapor was 8.0.times.10.sup.-4 to
6.0.times.10.sup.-2 Pa. Note that oxygen was not introduced. The
substrate temperature at the time of film formation was 25.degree.
C.
[0111] With regard to the obtained film, the Hall effect was
measured. The result is illustrated in FIG. 3, in which the
dependence of the carrier density, the Hall mobility, and the
resistivity of the In--Ga--Zn--O film on the partial pressure of
water vapor when the film was formed by sputtering is illustrated.
By introducing a partial pressure of water vapor of
1.times.10.sup.-2 Pa or higher, the resistivity of the
In--Ga--Zn--O film could be increased. Further, the carrier density
could be made to be 1.times.10.sup.18 cm.sup.-3 or less. With
regard to the In--Ga--Zn--O film, X-ray diffraction was carried out
with the incident angle upon a film surface being as small as about
0.5 degrees. With regard to all the cases, no clear diffraction
peak was observed, and it was confirmed that the prepared
In--Ga--Zn--O film was an amorphous film. Further, AFM measurement
was performed and the pattern was analyzed to find that the surface
roughness (Ra) of the thin film was about 0.4 nm. The film
thickness was about 200 nm. As a result of X-ray photoelectron
spectroscopy (XPS) analysis, it was found that the composition
ratio of the metals in the thin film was In:Ga:Zn=1:1:0.9.
[0112] Further, a 3-inch sized sintered body of InZnO (ZnO: 10.7 wt
%) was used as the target (material source) and similar experiment
was carried out. By introducing a partial pressure of water vapor
of 1.times.10.sup.-2 Pa or higher, the resistivity of the InZnO
film could be increased, and an amorphous IZO film could be
obtained.
[0113] With regard to the obtained amorphous In--Ga--Zn--O film and
the IZO film, secondary ion mass spectrometry (SIMS) measurement
was performed to quantify the amount of hydrogen in the films. The
result is illustrated in FIG. 10. It was found that, in the films,
according to the partial pressure of the introduced water vapor,
hydrogen of 1.times.10.sup.21 to 1.times.10.sup.22 cm.sup.-3, which
is more than 1.times.10.sup.20 cm.sup.-3 according to the present
invention, was contained. Further, because the double logarithmic
plot of the amount of hydrogen in the film and the partial pressure
of the introduced water vapor exhibits very good linearity, it was
found that the amount of hydrogen in the film could be precisely
controlled by the partial pressure of the introduced water
vapor.
Example 2
[0114] In this example, another embodiment of a TFT device of the
present invention is described with reference to FIG. 9.
[0115] First, as a channel layer, an In--Ga--Zn--O film 903 was
formed on an n-type low resistance silicon substrate 900 having a
thermally grown silicon oxide film 904 at a thickness of 100 nm
formed thereon. By DC sputtering in an argon atmosphere, the
In--Ga--Zn--O film was formed.
[0116] As the target (material source), a 3-inch sized sintered
body having a composition of InGaZnO.sub.4 was used, and the
applied RF power was 50 W. The distance between the target and the
substrate was 60 mm. The In--Ga--Zn--O film was formed in an
atmosphere of argon-water vapor mixed gas at 5.0.times.10.sup.-1 Pa
with the partial pressure of the introduced water vapor being
6.2.times.10.sup.-2 Pa. It is to be noted that oxygen was not
introduced. The temperature of the substrate when the film was
formed was 25.degree. C. The thickness of the amorphous
InGaZnO.sub.4 channel layer was 30 nm. After that, the channel
layer was patterned by photolithography. Then, electron beam
heating vapor deposition was used to laminate a Ti layer at a
thickness of about 5 nm and an Au layer at a thickness of about 100
nm from a side nearer to the channel layer in this order, and a
source electrode 902 and a drain electrode 901 were formed by
photolithography and lift-off. In this way, a bottom gate reverse
stagger TFT having a channel length of 30 .mu.m and a channel width
of 180 .mu.m was completed. In this TFT device, the n-type low
resistance silicon film 900 functions as a gate electrode 905 while
the thermally grown silicon oxide film 904 at a thickness of 100 nm
functions as a gate insulating layer.
[0117] Next, characteristics of the TFT device obtained in this way
were evaluated. FIG. 11 illustrates Id-Vg characteristics (transfer
characteristics) of the TFT device prepared in this example, which
were measured at room temperature when Vd=20 V with regard to a
case with no thermal treatment after the TFT was formed, a case
with thermal treatment at 200.degree. C. for 30 minutes in the
atmosphere, and a case with thermal treatment at 250.degree. C. for
30 minutes. It was found that the resistivity of the amorphous
InGaZnO.sub.4 channel layer could be controlled only by the partial
pressure of the water vapor, and that the TFT device had an on/off
ratio comparable to a transistor and a TFT characteristic of
10.sup.4 or more.
Example 3
[0118] In this example, another embodiment of a TFT device of the
present invention is described with reference to FIG. 4.
[0119] First, an Mo electrode as a gate electrode was formed on a
glass substrate 10 by sputtering. Then, patterning was carried out
by photolithography. After an SiO.sub.2 film as a gate insulating
film 14 was formed by sputtering, a source electrode 12 and a drain
electrode 11 were formed. Then, similarly to the case of Example 2,
an In--Ga--Zn--O film was formed thereon as a channel layer 13. The
thickness of the amorphous InGaZnO.sub.4 channel layer was 30 nm.
The partial pressure of the introduced water vapor was
1.6.times.10.sup.-2 Pa, 6.2.times.10.sup.-2 Pa, and
8.6.times.10.sup.-2 Pa. It is to be noted that oxygen was not
introduced. The temperature of the substrate when the film was
formed was 25.degree. C.
[0120] Further, an SiO.sub.2 film as a protective film 16 was
deposited thereon at a thickness of 100 nm by sputtering.
[0121] In this example, the applied RF power was 300 W. The
atmosphere at the time of film formation was such that the total
pressure was 0.1 Pa, and the gas flow rate ratio was
Ar:O.sub.2=90:10. The substrate temperature was 25.degree. C.
[0122] Finally, contact holes were formed by removing a part on
each of the gate electrode 15, the drain electrode 11, and the
source electrode 12 by photolithography and etching. Then, thermal
treatment was carried out at 250.degree. C. for 60 minutes in the
atmosphere. In this way, a bottom gate TFT having a channel length
of 30 .mu.m and a channel width of 180 .mu.m was completed.
[0123] Next, characteristics of the thus obtained TFT device were
evaluated. FIG. 5 is a graph illustrating the Id-Vg characteristics
(transfer characteristics) at Vd=20 V of the TFT device produced in
this example when the measurement was carried out at room
temperature. A current of about Id=1.times.10.sup.-5 A flowed at
Vd=20 V. In addition, the field-effect mobility was calculated from
the output characteristics under the partial pressure of the
introduced water vapor of 8.6.times.10.sup.-2 Pa to yield a
filed-effect mobility of approximately 3 cm.sup.2/Vs in the
saturation region.
Example 4
[0124] In this example, a display apparatus using a thin film
transistor illustrated in FIG. 12 is described. The process of
forming a channel layer in the thin film transistor used is similar
to that in the case when the partial pressure of the introduced
water vapor was 8.6.times.10.sup.-2 Pa in Example 3.
[0125] In the above-mentioned thin film transistor, after an
insulating layer (protective layer) 16 covers and is patterned, a
short side of an island of an ITO film forming a drain electrode 12
is extended to be 100 .mu.m, and the extended portion having the
length of 90 .mu.m is left to secure wiring to a source electrode
11 and to a gate electrode 15. A polyimide film is applied thereon
and a rubbing process is carried out. Meanwhile, similarly, a
plastic substrate having an ITO film and a polyimide film formed
thereon and which then undergoes a rubbing process is prepared, and
is opposed to the above-mentioned substrate having the thin film
transistor formed thereon with a gap of 5 .mu.m therebetween, and
nematic liquid crystal is injected into the gap. Further, a pair of
polarizing plates are provided such that one of the polarizing
plates is on one side of the structure and the other of the
polarizing plates is on the other side of the structure. Here, when
voltage is applied to the source electrode of the thin film
transistor and voltage applied to the gate electrode is changed,
the light transmittance changes only in a region of 30
.mu.m.times.90 .mu.m which is a part of the island of the ITO film
extended from the drain electrode. Further, the transmittance may
be continuously changed also by source-drain voltage when gate
voltage is applied such that the thin film transistor is turned on.
In this way, a display apparatus corresponding to the one
illustrated in FIG. 7 and having a liquid crystal cell as a display
device is prepared. It is to be noted that FIG. 12 also illustrates
a substrate 10, a channel layer 13, and a gate insulating film
14.
[0126] In this example, a white plastic substrate is used as the
substrate on which the thin film transistor is formed. The
electrodes of the thin film transistor are replaced by gold, and
the polyimide film and the polarizing plates are eliminated. A
capsule having particles and fluid encapsulated in an insulating
film thereof is made to fill the gap between the white and
transparent plastic substrates. In the case of this display
apparatus having the above-mentioned structure, voltage between the
drain electrode extended in the thin film transistor and the upper
ITO film is controlled, thereby moving up and down the particles in
the capsule. Therefore, by controlling the reflectivity in the
extended drain electrode region seen from the side of the
transparent substrate, display may be carried out.
[0127] Further, in this example, a plurality of thin film
transistors may be formed so as to be adjacent to one another to
form a current control circuit having, for example, a popular
structure including four transistors and one capacitor with one
transistor at the last stage thereof being the thin film transistor
illustrated in FIG. 12 to drive EL devices. For example, a thin
film transistor with the above-mentioned ITO film being used as a
drain electrode thereof is used. An organic electroluminescent
device including an electron injection layer and an emission layer
is formed in the region of 30 .mu.m.times.90 .mu.m which is a part
of the island of the ITO film extended from the drain electrode. In
this way, the display apparatus using EL devices illustrated in
FIG. 6 may be formed.
Example 5
[0128] In this example, the display devices and the thin film
transistors of Example 4 are disposed two-dimensionally. For
example, pixels each occupying an area of about 30 .mu.m.times.115
.mu.m including the display device such as a liquid crystal cell or
an EL device and the thin film transistor of Example 4 are disposed
at a pitch of 40 .mu.m in a direction of a short side and at a
pitch of 120 .mu.m in a direction of a long side are disposed so as
to form a rectangle of 7,425.times.1,790 pixels. Further, 1,790
gate wirings which go through gate electrodes of 7,425 thin film
transistors in the direction of the long side and 7,425 signal
wirings which go, in the direction of the short side, through
portions of the source electrodes of 1,790 thin film transistors
extended by 5 .mu.m from the island of the amorphous oxide
semiconductor film are provided, and are connected to a gate driver
circuit and a source driver circuit, respectively. In the case of a
liquid crystal display device, by providing on a surface thereof a
color filter of the same size as the liquid crystal display device
and which is aligned with the liquid crystal display device and by
repeatedly providing such color filters of RGB in cycles in the
direction of the long side, an A4-sized active matrix color image
display apparatus with about a 211 ppi resolution may be
formed.
[0129] In the case of an EL device, a gate electrode of a first
thin film transistor of two thin film transistors included in one
EL device is connected to a gate line while a source electrode of a
second thin film transistor is connected to a signal line. Further,
the light emitting wavelength of the EL device is changed in cycles
in RGB in the direction of the long side. In this way, a light
emitting color image display apparatus with the same resolution may
be formed.
[0130] Here, the driver circuits for driving the active matrix may
be formed using the thin film transistors according to the present
invention which are the same as the thin film transistors of the
pixels, or may be formed using existing IC chips.
[0131] While the present invention has been described with
reference to exemplary embodiments, it is to be understood that the
invention is not limited to the disclosed exemplary embodiments.
The scope of the following claims is to be accorded the broadest
interpretation so as to encompass all such modifications and
equivalent structures and functions.
[0132] This application claims the benefit of Japanese Patent
Application No. 2008-219888, filed Aug. 28, 2008, which is hereby
incorporated by reference herein in its entirety.
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